JPS61238809A - Liquid photosensitive polyimide resin composition - Google Patents

Abstract

PURPOSE:The titled liquid resin composition which can give a photocured film excellent in heat resistance, wet adhesion resistance, galvanic corrosion resistance, mechanical strength, etc., obtained by mixing a specified organic solvent- soluble photosensitive polyimide with an organosilane compound and an organic polar solvent. CONSTITUTION:The titled liquid resin composition is prepared by mixing 100pts. wt. organic solvent-soluble photosensitive polyimide (A) obtained by polymerizing a tetracarboxylic acid based on a biphenyltetracarboxylic acid with an aromatic diamine component based on an aromatic diamine of formula I (wherein Ar1 is a bivalent aromatic group and R1 is a photosensitive group-containing substituent), e.g., metharyloyloxyethyl 3,5-diaminobenzoate) with 1-25pts.wt. organosilane compound (b) of formula II (wherein R2 is H or methyl, R3 is methyl of ethyl and n is 0-3) and 200-3,000pts.wt. organic polar solvent (C) (e.g., N,N-dimethylformamide).

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a specific photosensitive material that is soluble in an organic solvent and has a photosensitive group in the polymer chain of polyimide that has the ability to crosslink by irradiation with light. It relates to a photosensitive polyimide resin liquid composition containing polyimide, a specific organic silane compound, and an organic polar solvent, and this resin liquid composition includes:
It can be used as a forming material for insulating films, passivation films, or liquid crystal alignment films for solid-state devices in the semiconductor industry, and has excellent moisture-resistant adhesion to 5t02, A12 03, silicon wafers, transparent electrodes (CITO'), etc. It is possible to form a photocured film (protective film) showing the following properties.

[Description of known technology]

Traditionally, Si3N4 has been mainly used as a material for insulating films used in the semiconductor industry, etc.
When a film is formed using a chemical vapor deposition method, the surface of the film exhibits unevenness that is in phase with the surface of the substrate, so advanced techniques are required to correct the unevenness in subsequent steps, making operations complicated. It will become.

Recently, a method of forming a heat-resistant photocured film using a photosensitive polymer instead of 5iiNz has been proposed (Japanese Unexamined Patent Application Publication No. 116216/1983,
-116217, JP 55-45747, JP 56-45915, JP 57-170
929, and Japanese Patent Application Laid-open No. 143341/1982), these known methods form a thin film from a solution of polyamic acid, which is a precursor of polyimide, and After the thin film is photocured, it is necessary to imidize the polymer that makes up the thin film at a fairly high temperature, which makes it difficult to form a film with stable quality and high heat resistance. This method has the drawback of thermally deteriorating the material layer (wiring pattern), etc. Further, the polyamic acid solution is
There were also problems with long-term storage stability.

Furthermore, films formed by methods using known photosensitive polymers did not have sufficient moisture-resistant adhesion to surfaces such as 5i02, Al103, silicon wafers, and transparent electrodes (ITO").

On the other hand, in the semiconductor industry as mentioned above, various methods using organic silane compounds have been proposed and commonly used to improve the adhesion of films to surfaces such as substrates, but photosensitive polymers, especially When an organic silane compound is blended into a photosensitive polyimide resin liquid composition for a polyimide film, it may not necessarily contribute sufficiently to improving the adhesion of the film, or the photosensitive polyimide resin liquid composition may be denatured. However, there was a problem in that the storage stability was significantly deteriorated.

[Requirements of the present invention and its effects]

The inventors were able to solve various problems such as stability of the resin liquid and adhesion of the film when forming a heat-resistant coating layer using a resin liquid composition of a photosensitive polymer. As a result of extensive research on resin liquid compositions, we found that a photosensitive polyimide containing a specific organic solvent-soluble photosensitive polyimide that has a photosensitive group within the polymer chain of the polyimide, a specific organic silane compound, and an organic polar solvent was developed. The present invention was completed based on the discovery that a polyimide resin liquid composition has extremely suitable performance.

That is, this invention provides a tetracarboxylic acid component mainly containing biphenyltetracarboxylic acids, (wherein A r H represents a divalent aromatic residue of an aromatic diamine compound, and R1 represents a photosensitive group. 100 parts by weight of an organic solvent-soluble photosensitive polyimide obtained by polymerizing an aromatic diamine component mainly containing an aromatic diamine compound represented by the general formula (where R2 is a hydrogen atom or is a methyl group, R
3 is a methyl group or an ethyl group, and n is 0
It is an integer of ~3. )Organosilane compounds 1~
The present invention relates to a photosensitive polyimide resin liquid composition comprising 25 parts by weight and 200 to 3000 parts by weight of an organic polar solvent.

The resin liquid composition of the present invention is applied to the surface of an object to be coated to form a coating film of the resin liquid composition of uniform thickness, and the coating film is dried to form a photosensitive polyimide film. The photosensitive polyimide film is a photosensitive film having high sensitivity and resolution when photocured by irradiation with light, and furthermore, the photosensitive polyimide film has high sensitivity and resolution when photocured by irradiating light. By curing, a heat-resistant photocurable polyimide film (protective film) can be formed at a relatively low temperature.

The resin liquid composition of the present invention is a liquid composition that has excellent long-term storage stability, and the photocured film formed from this resin liquid composition is made of 5i02, Al2O3, silicon wafer, transparent electrode ( It has excellent adhesion to objects to be coated such as ITO, particularly moisture-resistant adhesion, and also has excellent electrical corrosion resistance and mechanical strength.

[Detailed explanation of each requirement of the present invention]

The photosensitive polyimide used in this invention contains about 70 mol% or more of biphenyltetracarboxylic acids, particularly 80 mol% or more of biphenyltetracarboxylic acids.
and a tetracarboxylic acid component containing about 100 mol% (wherein, Ar1 represents a divalent aromatic residue of an aromatic diamine compound, and R represents a substituent having a photosensitive group). About 50 mol% of the aromatic diamine compound
or more, preferably 50 to 90 mol%, particularly preferably 6
It is an organic solvent-soluble photosensitive polyimide obtained by polymerizing an aromatic diamine component containing about 0 to 85 mol%.

The aromatic diamine component used in the production of the photosensitive polyimide mainly contains an aromatic diamine compound having a photosensitive group represented by the general formula (r),
In order to improve various properties (for example, storage stability, solubility, mechanical performance, etc.) of photosensitive polyimide resin liquid compositions, in addition to the aromatic diamine represented by the general formula (1), photosensitive It may contain less than about 50 mol %, particularly preferably about 10 to 50 mol %, of other aromatic diamines that do not have groups, and in that case, if the blending ratio of aromatic diamines that have photosensitive groups is too small. If it is too high, the photosensitive polyimide obtained from such an aromatic diamine component will have a decreased photosensitivity during photocuring, which is not preferable.

In this invention, the aromatic diamine represented by the general formula (1) includes 3,5-diaminobenzoic acid methacryloyloxyethyl ester, 3,5-diaminobenzoic acid acryloyloxyethyl ester, and 2,4-diaminobenzoic acid methacryloyl ester. oxyethyl ester, 3,5-diaminobenzoic acid methacryloyloxypropyl ester,
Benzoic acid esters such as 2.4-diaminobenzoic acid methacryloyloxypropyl ester, 3.5-diaminobenzoic acid methacryloyloxyglycidyl ester, 2.4-diaminobenzoic acid methacryloyloxyglycidyl ester, or 3.5-diaminobenzyl acrylate, 3,5-diaminobenzyl methacrylate,
Examples include 2,4-diaminobenzyl acrylate and 2,4-diaminobenzyl methacrylate.

In addition, other aromatic diamines not having the above-mentioned photosensitive group include toxylylene diamine, p-xylylene diamine, 4.4°-diaminodiphenyl ether, 3.4°-diaminodiphenyl ether,
''-diaminodiphenyl ether, p-fuynylene diamine, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 0-tolidine, todiaminodiphenylsulfone, and the like.

The biphenyltetracarboxylic acids mainly contained in the tetracarboxylic acid component used in the production of the photosensitive polyimide are, for example, 3.3'-, 4.4'-
Biphenyltetracarboxylic acid or its acid dianhydride, 2
．． 3.3°, 4'-biphenyltetracarboxylic acid or its acid dianhydride, or esters or salts of these acids, particularly 2.3, 3°, 4'-biphenyltetracarboxylic acid, etc.
”-biphenyltetracarboxylic dianhydride is most suitable.

The above-mentioned tetracarboxylic acid component may contain, in addition to biphenyltetracarboxylic acids, other aromatic tetracarboxylic acids or aliphatic tetracarboxylic acids at about 30 mol% or less, particularly about 0 to 20 mol%. .

The photosensitive polyimide used in the present invention can be produced by any known production method.
Polyamic acid is polymerized in a polar solvent at a polymerization temperature below about 80°C, particularly below 60°C, and a polymerization time between about 0.5 and 50 hours, especially between 1 and 30 hours, and then acetic anhydride, Preferably, the polyamic acid is imidized to produce polyimide by using an imidizing agent such as pyridine or tertiary amine or by heating to a high temperature.

Examples of the organic polar solvent used in the method for producing photosensitive polyimide include N,N-dimethylsulfoxide, N,
Examples include N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoramide, and the like.

The photosensitive polyimide used in this invention has a logarithmic viscosity (concentration: 0.5 g/100v+J solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30°C) of 0.1 to
4, particularly preferably about 0.2 to 2.

The photosensitive polyimide resin liquid composition of the present invention includes 100 parts by weight of the photosensitive polyimide and 1 to 25 parts by weight, preferably 5 to 20 parts by weight, of an organic silane compound represented by the general formula (■).
parts by weight, and 200 to 3000 parts by weight of an organic polar solvent,
Preferably, the resin liquid composition contains 250 to 2,500 parts by weight.

If the amount of the organic silane compound used is too small, the photocured film formed from such a resin liquid composition will not have sufficient adhesion to the object to be coated, especially moisture resistant adhesion, and this is not appropriate. However, if the amount of the organic silane compound used is too large, the storage stability of the resin liquid composition will decrease, which is not appropriate.

In this invention, the organosilane compound has an acryloyl-amino group or a methacryloyl-amino group at at least one end of the molecular chain of the organosilane compound, and a trialkoxysilyl group at the other end. It is characterized in that it is a specific organic silane compound represented by the general formula (II), and when other organic silane compounds are used, it is formed by forming a film from such a resin liquid composition and photocuring. This is not suitable because the resulting coating does not exhibit sufficient adhesion performance to the object to be coated or the storage stability of the resin liquid composition is impaired.

Examples of the organic silane compound include N-(3-trimethoxysilyl-propyl-acrylamide, N-
(3-) ethoxysilyl-propyl]-acrylamide, N-[3-trimethoxysilyl-propyl-methacrylamide, N-(3-triethoxysilyl-propyl-methacrylamide, N-(2-(3- trimethoxysilyl-propyl-amino)-ethyl]-acrylamide, N-(2-(3-1-ethoxysilyl-propylamino)-ethyl)-acrylamide, N-(2-
Examples include (3-1-rimethoxysilylpropylamino)-ethyl]-methacrylamide, N-(2-(3-triethoxysilyl-propyl-amino)-ethyl)-methacrylamide, and the like.

As the organic polar solvent used in this invention, the organic polar solvent used as a polymerization solvent in the production of the photosensitive polyimide described above can be used almost as it is, and in particular, N,
N-dimethylformamide, N.

Preferred examples include N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylene phosphoamide, and the like.

In addition to the above-mentioned solvents, a mixed solvent containing xylene, ethyl cellosolve, diglyme, dioxane, etc. can also be used. The concentration of photosensitive polyimide in the resin liquid composition of the present invention is approximately 4 to 30% by weight, particularly 5% by weight.
Preferably it is 25% by weight.

Furthermore, the resin liquid composition of the present invention may contain a known photosensitizer or photopolymerization initiator, such as Michlerske, Ton, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl , α,α-dimethoxybenzylphenylketone, 2-t-butylanthraquinone, l,2-benzo-9,10-anthraquinone, 4,4゛-bis(diethylamino)benzophenone, acetophenone, benzophenone, benzophenonethioxanthone, 2.4 −
Diethylthioxanthone, 1.5-acenaphthene, N
-acetyl-4-nitro-1-naphthylamine, 4.4
-Diazidochalcone, 4,4"-Diazidodibenzalacetone, 2,6-di(4'-azidobenzal)cyclohexanone, 2,6-di(4°-azidobenzal)-4-
Examples include methylcyclohexanone, 4,4'-diazidostilbene, and in some cases, N,N-
A sensitizing aid such as methyl dimethylanthranilate or ethyl N,N-dimethylaminobenzoate may also be added.

Furthermore, the resin liquid composition of the present invention may contain a known photopolymerizable monomer, particularly a monomer compound having an ethylenically unsaturated group, and may also contain a polymerization inhibitor to increase polymerization stability during heating. can be added.

Examples of the photopolymerizable monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, N,N-methylenebis (meth)acrylate, diethylaminoethyl (meth)acrylate, 1゜3.5-triacryloylhexahydro-5-)riazine, tris(hydroxyethylacryloyl)isocyanurate, 1.3.5-1-remethacryloyl Examples include quinoa draw 3-triazine. In addition, examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2.
Examples include 6-di-t-butyl-p-cresol.

As a method for forming a pattern consisting of a photocured film using the resin liquid composition of the present invention, for example, first, the above-mentioned photosensitive polyimide resin liquid composition is coated with a spin coating machine, a roll coater, etc. The resin liquid composition is applied to the surface of the substrate with the printed wiring pattern to form a coating film, and the coating film is dried at about 150°C or lower, preferably 100°C or lower, and under normal pressure or reduced pressure if necessary. , an uncured film of photosensitive polyimide is formed, a negative photomask chart is superimposed on the film, and active light such as ultraviolet rays, visible light, electron beams, or X-rays is irradiated onto the film. , a method of forming a polyimide relief pattern by photocuring and washing away the unexposed area (unphotocured area) of the film with a developer.

As the developer, a polymerization solvent used in producing the photosensitive polyimide or an organic polar solvent used in the resin liquid composition can be used. For example, N,N-dimethylformamide can be used as the developer. , N,N-dimethylacetamide, tomethyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylene phosphoamide, etc., and a mixed solvent of these solvents with methanol, ethanol, etc. can also be used. .

[Examples and reference examples]

Reference Example 1 [Manufacture of photosensitive polyimide] N-methyl-2-pyrrolidone (NMP) 31.3 mj!
, 6.067 g of 2,3.3",4'-biphenyltetracarboxylic dianhydride, and 3.842 g of 3,5-diaminobenzoic acid methacryloyloxyethyl ester,
Add 0.843 g of toxylylene diamine and heat at 20°C.
The mixture was stirred for 24 hours to carry out a polymerization reaction to produce polyamic acid. Next, 153.7 ml of NMP was added to the polyamic acid reaction solution to dilute it, and then 41.12 g of acetic anhydride, 15.93 g of pyridine, and 30.1 ml of benzene were added to the diluted solution, and the mixture was heated at 40°C for 4 hours. ,
An imidization reaction is carried out to produce photosensitive polyimide.Finally, methanol is added dropwise to this reaction solution to precipitate photosensitive polyimide in powder form, and the powder is filtered and separated to obtain white polyimide powder. Obtained.

Reference Example 2 [Manufacture of organic silane compound (A)] 6.64 g of 3-aminopro and root triethoxysilane (
30 mmol), 3.04 g (30 mmol) of triethylamine, and 150 ml of benzene were prepared.
Add 2.7 liters of acrylic acid chloride to the mixture under ice water cooling.
A reaction mixture was prepared by adding dropwise a mixture of 2 g (30 mmol) and 50 m Il of benzene. - Furthermore, after stirring the above reaction mixture at room temperature for 4.5 hours, 100 ml of water was added to separate the aqueous phase, the benzene phase was dried over anhydrous sodium sulfate, and the solution was The solvent was distilled off under reduced pressure to obtain about 5.70 g of the reaction product.
(69% yield).

The reaction product was found to be N-[3-triethoxysilyl-probyltoacrylamide as a result of various tests such as elemental analysis, infrared absorption spectroscopy, and NMR.

Reference Example 3 [Manufacture of organic silane compound (B)] The reaction was carried out in the same manner as in Reference Example 3, except that 2.72 g (30 mmol) of acrylic acid chloride was replaced with 3.14 g (30 mmol) of methacrylic acid chloride. The reaction product was obtained in a yield of about 6.62 g (76% yield).

The reaction product was found to be N-(3-)ethoxysilyluprobyl]-methacrylamide as a result of various tests such as elemental analysis, infrared absorption spectroscopy, and NMR.

Example 1 9.00 g of photosensitive polyimide produced in Reference Example 1,
1,3.5-) Rimethacryloylhesahydro-
3-) Lysine (photopolymerizable monomer) 1. OOg, N-(3-()ethoxysilyl)-brobyl]-acrylamide produced in Reference Example 2 (organosilane compound A) 0.
09 g, 2.6-di(4'-azidobenzal)-4
-Methylcyclohexane (photopolymerization initiator) 1.00g1
Hydroquinone 7-methyl ether (11℃ reaction inhibitor)
0.025 g, and organic polar solvent (NMP4o, o
A mixed solvent of 0 g and 4.50 g of diglyme) was mixed and dissolved to prepare a photosensitive polyimide resin liquid composition. This resin liquid composition has a rotational viscosity (25°C) of 220
It was a centiboise, and there was virtually no change in rotational viscosity even if it was left at room temperature for 10 days.

Comparative Example 1 Except that organosilane compound A was not used at all,
A photosensitive polyimide resin liquid composition was prepared in the same manner as in Example 1. This resin liquid composition has a rotational viscosity (2,5
℃) was 220 centivoise, and there was virtually no change in rotational viscosity or the like even after being left at room temperature for 10 days.

Comparative Example 2 A photosensitive polyimide resin liquid composition was prepared in the same manner as in Example 1, except that 0.27 g of γ-methacryloyloxy-propyl-trimethoxysilane was used instead of the organic silane compound A. This resin liquid composition has a rotational viscosity (2
5°C) was 220 centivoise, and there was virtually no change in rotational viscosity or the like even after being left at room temperature for 10 days.

Comparative Example 3 Organic silane compound A was changed to 0.09 g of γ-(2-aminoethyl)amino-propyl-trimethoxysilane. When this resin liquid composition was left at room temperature, it solidified into an agar-like state and gelled 2 hours after preparation.

Example 2 Photosensitive polyimide 10.0 obtained by the same method as Synthesis Example 1
0 g, 1.3.5-)remethacryloyl-hesahydro-8-tolidine (photopolymerizable monomer) 1.10 g1
N-(3-t-ethoxysilylubrobyl)methacrylamide obtained in Reference Example 3 (Organic Silane Compound B)
0.27 g, 2.4-diethylthioxanthone (
Photopolymerization initiator) 0.40g, ethyl 4-(N,N-dimethylamino)benzoate (photosensitizer) 0.60g, hydroquinone monomethyl ether (polymerization inhibitor) 0.02
A photosensitive polyimide resin liquid composition was prepared by mixing and dissolving 5 g of the photosensitive polyimide and an organic polar solvent (a mixed solvent of 45.00 g of NMP and 5.00 g of diglyme). This resin liquid composition had a rotational viscosity (25° C.) of 220 centivoise, and there was virtually no change in the rotational viscosity even when it was left at room temperature for 10 days.

Example 3 Instead of 80.27 g of organosilane compound, N-(2-(
3-triethoxysilyl-propyl-amino)-ethyl-acrylamide (organosilane compound C) 0.10 g
A photosensitive polyimide resin liquid composition was prepared in the same manner as in Example 2, except that . This resin liquid composition has a rotational viscosity (25°C) of 200 centivoise and 1
Even after being left at room temperature for 0 days, there was virtually no change in rotational viscosity or the like.

Comparative Example 4 Example 3 except that the organosilane compound C was changed to 0.18 g of T-anilino-propyl-trimethoxysilane.
A photosensitive polyimide resin liquid composition was prepared in the same manner as above. This resin liquid composition has a rotational viscosity (25°C) of 23
0 centipoise, and there was virtually no change in rotational viscosity or the like even after being left at room temperature for 10 days.

Example 4 Photosensitization was carried out in the same manner as in Example 1, except that 0.18 g of N-(3-trimethoxysilyl-propyl)methacrylamide (organosilane compound D) was used in place of 0.09 g of organosilane compound A. A resin liquid composition of polyimide was prepared.This resin liquid composition had a rotational viscosity (at 25°C) of 2.
30 centipoise, and there was virtually no change in rotational viscosity or the like even after being left at room temperature for 10 days.

Comparative Example 5 Example 4 except that the organic silane compound was changed to 0.27 g of γ-mercaptopropyltrimethoxysilane.
A photosensitive polyimide resin liquid composition was prepared in the same manner as above. This resin liquid composition has a rotational viscosity (25°C) of 22
0 centipoise, and there was virtually no change in rotational viscosity or the like even after being left at room temperature for 10 days.

Forming a coating film on each substrate using the resin liquid composition obtained in each Example and each Comparative Example (excluding Comparative Example 3),
Then, the coating film was dried to form a photosensitive polyimide film with a thickness of about 2.5 μm, and these films were tested for photosensitivity, resolution, and after photocuring using the following test methods. The pencil hardness and adhesion to the surfaces of 5i02, silicon wafer, and Al1203 substrates were measured, and the results are shown in Table 1.

(a) Photosensitivity ~ Using a spin coating machine, apply the resin liquid composition onto the surface of the copper foil on the substrate, and dry it for 10 minutes in a hot air dryer at about 60°C to form a photosensitive polyimide coating ( A film with a thickness of approximately 2.5 μm) was formed, and a Kodak 21-stage step tablet (manufactured by Kodak, Grayscale N02) was superimposed and adhered to the film, and an ultra-high pressure mercury lamp (Jet Light 2kW, manufactured by Iwasaki Electric ■) was placed on top of the film. After irradiating with light at a light intensity of 5 J/-, development is performed using a developer (NMP) to remove the resin in the uncured areas that were not irradiated with light, and the amount of light irradiation until photocuring is determined. Measure and calculate the light sensitivity value (
The unit HJ/aJ) was calculated.

φ) Resolution Regarding the photosensitive polyimide coating (2.5 μm) formed in the same manner as the method for measuring photosensitivity, negative test chart (manufactured by Toppan Printing ■, Trapan Test Chart) N, minimum line width: 0.98 ±0.25. um) were superimposed and subjected to light irradiation and development in the same manner as in the method for measuring photosensitivity to form a photocured relief pattern, and the quality of the pattern was observed and determined.

(Photocuring was performed in the same manner as the photosensitivity measurement method, except that the light irradiation amount was twice the amount of light that indicated the photosensitivity measured in the C1 pencil hardness sensitivity measurement, and the photocured film was heated to 200°C. The sample was heat-treated for 2 hours in a thermal open environment, and the sample was JIS 0
Pencil hardness was measured according to method 8.10 of 0202.

(d) Adhesive St O2, silicon wafer, An! A photosensitive polyimide film was formed on the surface of the substrate No. 203 in the same manner as the photosensitivity measurement method, and after irradiating the film with twice the amount of light that satisfied the photosensitivity of the film, it was incubated at 200°C. The sample was heat-treated for 2 hours in a hot open environment, and the sample was immersed in boiling water for 2 hours, and the adhesion immediately after was measured according to JIS DO
It was measured according to the method of 8.12 (base test) of 202.

Claims (1)

[Claims] A tetracarboxylic acid component mainly containing biphenyltetracarboxylic acids, and a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (However, Ar_1 is a divalent aroma of an aromatic diamine compound. 100 weight of an organic solvent-soluble photosensitive polyimide obtained by polymerizing an aromatic diamine component mainly containing an aromatic diamine compound shown in General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_2 is a hydrogen atom or a methyl group,
R_3 is a methyl group or an ethyl group, and n is an integer of 0 to 3. 1 to 25 parts by weight of an organic silane compound shown in ) and 200 to 3000 parts by weight of an organic polar solvent.